Stretchable aqueous-based Zn-ion batteries have shown promise as a sustainable and safe energy storage system for wearable electronics used in healthcare, sports, soft robotics, and prosthetics. A battery consists of the active electrode, electrolyte, current collector, and encapsulation. In this work, we focus on the development of the electrolyte component, which is a hydrogel based on polymers. Natural polymers (e.g proteins, polysaccharides) are chosen over synthetic ones because they are biodegradable, abundant in nature, and environmentally sustainable. Here, a hydrogel based on gelatin (G) and kappa-carrageenan (kC) were prepared and evaluated. We observed that the addition of kC into the hydrogel composite improved its mechanical properties. Optimum conditions at weight ratios of G:kC -99:1 wt%, the hydrogel showed good mechanical strength with an elongation at break of 370 ± 28%, elastic modulus of 0.119 ± 0.0256 MPa, and reversibility during 100 cyclic stretching at 50% strain. The hydrogel had a reasonable ionic conductivity of 14.80 mS/cm and was successfully integrated into a battery with a capacity of 0.24 mA/cm2. / <p>Examensarbetet är utfört vid Institutionen för teknik och naturvetenskap (ITN) vid Tekniska fakulteten, Linköpings universitet</p>

Casting, Solidification, Aluminum, Physical Metallurgy, Mechanical Metallurgy, Strengthening Model, Aluminum Wrought Alloys, Aluminum 7xxx Series, Al-Zn-Mg-Cu / Over the past decades, researchers in casting fields, especially in semi-solid metal state, have endeavored to find new ways to enable the Al wrought alloys of casting using the conventional casting processes; mainly in order to improve the product properties and decrease the product cost. The thixoforming and rheocasting processes have been presented as ways by which the microstructure of Al-base wrought alloys can be changed into non-dendritic, which in turn can lead to improvement to the mechanical properties. This can be because the effect of the non-dendritic microstructure on the mechanical properties of the material. Unfortunately, these processes have proved to be cost prohibitive and be a bit complicated for commercial applications. Further, conventional casting of Al-base wrought alloys along with their superior properties and performance have been a challenge for foundry industry due to the main disadvantage of hot tearing or hot cracking during solidification process. This can render the cast component ineffective. To overcome the disadvantages of thixoforming and rheocasting processes, Controlled Diffusion Solidification (CDS) process was innovated mainly to enable casting of aluminum wrought alloys with a non-dendritic morphology of the primary Al phase in the resultant cast microstructure and thus alleviating the problem of hot tearing and obtaining a cost effective product with improved mechanical properties. The CDS is a simple process involving mixing of two precursor alloys of different thermal masses (temperature and solute) and subsequently casting the resultant mixture of the desired solute composition and temperature as a near net shaped cast product. The process can easily be commercialized with a marginal capital cost required for set up such as the addition of an extra holding furnace. Further, the CDS process would prove itself to be unique in its ability to cast Al-based wrought alloys into near net shaped components without additional processes and cost. The originality of this study is to present a viable casting process for the Al-7xxx wrought alloys (Al-Zn-Mg-Cu); by which the Al-7xxx family alloys are presented in cast condition to have an acceptable uniaxial property range that is comparable with their wrought counterparts. This study presents the process and alloy parameters necessary for the casting of Al-7xxx wrought alloys (Al-Zn-Mg-Cu), by using the CDS process coupling with tilt pour gravity casting (TPGC) machine. The uniaxial tensile mechanical properties of several Al-7xxx CDS castings under various heat treatment conditions, namely, solutionizing (T4), peak aged (T6) and annealing (O), necessary for development of an ageing process on the material were investigated and presented. The tilt pour gravity casting process coupled with the CDS technology was employed to demonstrate the ability to cast Al-7xxx wrought alloys into high integrity components with high strength and ductility. The microstructure characterization was carried out by Electron Microscopy (TEM, SEM and EDS) and DSC test experiments for all the as cast (F), T4, T6 and anneals (O) conditions of the CDS cast components. Also, the predictive capabilities for the yield strength of Al 7xxx alloys CDS cast components was investigated using structural-properties modeling for the various strengthening effects that are recently proposed specifically for the Al-7xxx wrought counterparts. The study has successfully led to a more in-depth understanding of the innovative CDS casting process by applying it to several compositions of Al-7xxx wrought alloys in an industrial scale CDS casting experiments, using tilt pour gravity casting (TPGC) machine. This will hopefully lead us to a clearer path towards commercializing the CDS process and obtaining a viable casting process for Al-base wrought alloys into near net shape components without much change to economics of the casting process. / Dissertation / Doctor of Philosophy (PhD) / Casting, Solidification, Aluminum, Physical Metallurgy, Mechanical Metallurgy, Strengthening Model, Aluminum Wrought Alloys, Aluminum 7xxx Series, Al-Zn-Mg-Cu

This project was funded by Automotive Partnership Canada (APC), an initiative created by the Government of Canada in an attempt to support significant, collaborative R&D activities in order to benefit the entire Canadian automotive industry. / High strength Al-Zn-Mg-Cu alloys have been increasingly employed in the transportation industry due to the increased demands for light structural components. However, their applications have been limited to relatively expensive wrought products. Application of the shape cast Al-Zn-Mg-Cu parts has never been the focus of attention due to their poor castability and mechanical properties. Improving the casting quality is expected to increase their utilization within the automotive industry. The poor castability and mechanical properties of some alloys in this family may be effectively improved through optimized chemistry control and melt treatment including grain refinement. The primary objective of this project is to optimize the chemistry and heat treatment of the Al-Zn-Mg-Cu alloy family that results in improved strength with acceptable level of ductility and casting quality relative to other shape cast Al alloys. The Taguchi experimental design method was used to narrow down the number of required casting experiments required to meet the research objective. Three levels across four elements yielded a total of 9 Al-Zn-Mg-Cu alloys, which were cast using a tilt pour permanent mold process. The effect of each major alloying element on the microstructure, and mechanical properties was investigated. Tensile measurements were made on the 9 alloys subjected to two steps solution treatments. Mechanical properties such as yield strength (YS), ultimate tensile strength (UTS), and elongation at fracture (El.%) were experimentally measured and statistically analyzed. An ANOVA analysis was employed to quantify the percentage contribution of the alloying elements on the material properties. Grain refinement was found to play a significant role in improving the hot tearing resistance and, thereby ameliorating quality. The alloying element that affected the YS and UTS to the greatest extent was Cu, followed by Zn. In contrast, the effect of Mg and Ti on YS and UTS was insignificant. Moreover, a decrease in Mg content had the greatest effect in enhancing the El.%. A regression analysis was used to obtain statistical relationships (models) correlating the material properties with the variations in the content of the major alloying elements. The R-square values of YS, UTS, and El.% were 99.7 %, 98 %, and 90 %, respectively, showing that the models replicated the experimental results. Verification measurements made on shape cast Al-6Zn-2Mg-2Cu alloy revealed that the material property model predictions were in agreement with the experimentally measured values. The results show that secondary and over ageing treatments of the shape cast Al-Zn-Mg-Cu alloys lead to superior combination of YS and El.%. The ongoing advances in shape casting of Al-Zn-Mg-Cu alloys with high will make them suitable choices for commercial load-bearing automotive components, when it comes to the selection of a material meeting the minimum requirements for strength, damage tolerance, cost and weight. / Thesis / Master of Applied Science (MASc)

Al-Zn-Mg-Cu-Zr based AA7010 aluminum alloy belongs to the class of heat treatable alloys and the semi-finished products are generally produced by hot rolling, forging or extrusion processes. It is well known that the thermo-mechanical processing parameters strongly influence both the evolution of texture as well as microstructure in the material. As a result, the semi-finished products exhibit anisotropy in mechanical properties causing legitimate concerns on the applicability of the alloys. In the present thesis, a systematic study on the evolution of texture and microstructure and its implications on the mechanical properties anisotropy of AA7010 alloy has been attempted. A brief introduction on the development of texture and its influence on the anisotropy of the mechanical properties of 7xxx series aluminum alloys is presented first with a view to explore the scopes for further investigation. An overview of the relevant literature is described subsequently. The development of texture and microstructure in an Al-Zn-Mg-Cu-Zr based 7010 aluminum alloy during uneven, hot cross-rolling is presented. Materials processing involves three different types of uneven cross-rolling. The variations in relative intensity of the β-fibre components as a function of cross rolling modes have been investigated. It has been shown that the main attributes to the texture evolution in the present study are (a) cross-rolling and inter-pass annealing that reduce the intensity of Cu component following each successive pass, (b) recrystallization resistance of Bs oriented grains, (c) stability of Bs texture under cross-rolling, and (d) Zener pinning by Al3Zr dispersoids. The stability of the unique single, rotated Brass-{110}(556) component developed in the present alloy, during long term thermal annealing and cold rolling deformation has been systematically investigated further. Subsequently, the influence of development of microstructure and texture on the in-plane anisotropy (AIP) of yield strength, work hardening behavior and yield locus anisotropy has been presented. The AIP and work hardening behavior are evaluated by tensile testing at 0o, 45o and 90o to the rolling direction, whilst yield loci have been generated by Knoop hardness method. It has been observed that in spite of having strong rotated Brass texture, the specimens show low AIP especially in peak aged temper. The in-plane anisotropy (AIP) of yield strength, and work hardening behavior of a heat treated 7010 aluminum alloy sheet having strong, rotated Brass-{110}556 component with different texture intensity and volume fraction of recrystallization has been further evaluated. It is observed that the AIP increases with increase in texture intensity and volume fraction of recrystallization. In the subsequent chapter, the tensile flow and work hardening behavior are described using constitutive equations. Room temperature tensile properties have been evaluated as a function of tensile axis orientations in as-hot rolled as well as peak aged conditions. It has been found that both the Ludwigson and a generalized Voce-Bergström relation adequately describe the tensile flow behavior in all conditions compared to the Hollomon relation. The Voce-Bergström parameters define the slope of - plots in the stage-III regime when the specimens show a classical linear decrease in hardening. Further analysis of work hardening behavior throws light on the effect of texture on the dislocation storage and dynamic recovery. An overall summary of the experimental results and the scopes for future studies have been presented at the end.

Magnesium alloys have been widely explored as potential biomaterials, but several limitations to using these materials have prevented their widespread use, such as uncontrollable degradation kinetics which alter their mechanical properties. In an attempt to further the applicability of magnesium and its alloys for biomedical purposes, two novel magnesium alloys Mg-Zn-Cu and Mg-Zn-Se were developed with the expectation of improving upon the unfavorable qualities shown by similar magnesium based materials that have previously been explored. The overall performance of these novel magnesium alloys has been assessesed in three distinct phases of research: 1) analysing the mechanical properties of the as-cast magnesium alloys, 2) evaluating the biocompatibility of the as-cast magnesium alloys through the use of in-vitro cellular studies, and 3) profiling the degradation kinetics of the as-cast magnesium alloys through the use of electrochemical potentiodynamic polarization techqnique as well as gravimetric weight-loss methods. As compared to currently available shape memory alloys and degradable as-cast alloys, these experimental alloys possess superior as-cast mechanical properties with elongation at failure values of 12% and 13% for the Mg-Zn-Se and Mg-Zn-Se alloys, respectively. This is substantially higher than other as-cast magnesium alloys that have elongation at failure values that range from 7-10%. Biocompatibility tests revealed that both the Mg-Zn-Se and Mg-Zn-Cu alloys exhibit low cytotoxicity levels which are suitable for biomaterial applications. Gravimetric and electrochemical testing was indicative of the weight loss and initial corrosion behavior of the alloys once immersed within a simulated body fluid. The development of these novel as-cast magnesium alloys provide an advancement to the field of degradable metallic materials, while experimental results indicate their potential as cost-effective medical devices.

No description available.

Les alliages d'aluminium de la série 7000 à hautes caractéristiques mécaniques, constitués principalement des éléments d'addition Zn, Mg, et Cu, sont notamment utilisés dans l'industrie aéronautique civile. Néanmoins, les traitements thermiques et/ou thermomécaniques appliqués pour maximiser les propriétés mécaniques de ces alliages, peuvent les sensibiliser à divers modes de corrosion structurale dont la corrosion feuilletante, dont les mécanismes sont encore mal compris. En outre, les nouvelles générations d'alliages, développées en vue d'augmenter les propriétés mécaniques, contiennent toujours plus d'éléments d'addition, ce qui est susceptible de modifier leur sensibilité à ce phénomène. <br />Ce travail s'attache à faire progresser la compréhension des mécanismes de corrosion feuilletante des alliages 7000, en cherchant à identifier le rôle des principaux éléments d'alliage. Pour cela nous avons caractérisé finement les états de précipitation d'un grand nombre de microstructures, comme la composition des précipités durcissants nanométriques et de la matrice, par ASAXS et 3DAP. En parallèle, nous avons développé de nouvelles techniques électrochimiques permettant de quantifier la sensibilité de ces mêmes microstructures à la corrosion feuilletante. <br />Les résultats de l'étude mettent en évidence l'existence de deux mécanismes de corrosion : endommagement par dissolution intergranulaire et par rupture intergranulaire, dont la prédominance dépend de la composition de l'alliage et du traitement thermique. Nous proposons une explication au comportement en corrosion des différentes microstructures, faisant intervenir la composition chimique des différentes entités microstructurales.

Sur le site minier de Milluni (Bolivie, Altiplano, 4800 m asl), la contamination des eaux de surface et des sédiments par les métaux lourds a été étudiée en combinant des approches géochimiques, minéralogiques et hydrochimiques. Pour les différents métaux, les sources minérales de la contamination ont été établies, ainsi que les processus géochimiques d'altération des minéraux primaires en minéraux tertiaires. La compréhension des mécanismes géochimiques en jeu et les bilans réalisés ont permis de déterminer les origines et les modes de transport et de contrôle des métaux dans cet environnement. Enfin, les carottages des sédiments lacustres et des tourbières ont permis d'évaluer l'évolution historique de la contamination en métaux lourds, notamment au cours du siècle dernier.

Der Schwerpunkt der vorgelegten Arbeit lag in der Bestimmung der Energieniveaus an allen Grenzflächen in bestimmten heterostrukturierten Polymer/Polymer- und Polymer/Molekül basierten Solarzellen. Die elektronische Charakterisierung erfolgte mittels Photoelektronenspektroskopie. Morphologie und Schichtdicke der aufgeschleuderten Filme wurden mit den komplementären Analysetechniken UV-vis Absorptionsspektroskopie, Rasterkraftmikroskopie sowie Röntgenphotoelektronenspektroskopie bestimmt. An der PEDT:PSS-Anode/Polymer-Grenzschicht wurden Änderungen im Vakuumniveau von bis zu 0,65 eV gemessen. Die Polymerabscheidung führte zu einer Erniedrigung der Substrataustrittsarbeit, auch wenn die Polymerionisationsenergie mehrere 100 meV größer als die ursprüngliche PEDT:PSS-Austrittsarbeit war. Eine detailierte Analyse der PEDT:PSS/Polymer Grenzflächen ausgehend von Submonolagen zu Multilagen zeigte verschiedene Ursachen für die Änderungen des Vakuumniveaus als verantwortlich. Zweitens: an Donator/Akzeptor-Grenzflächen wurden Änderungen im Vakuumniveau von bis zu 0,35 eV festgestellt, welche die solare Bandlücke (PVG) und folglich die Höchstgrenze der Leerlaufspannung (VOC) beeinflusst. Ein Vergleich aller Resultate der Grenzflächenanalyse mit den Solarzellen Parametern bestätigte PVG als obere Schranke von VOC. Der Energieunterschied zwischen PVG und VOC, der ein Maß für die Verluste in der Solarzelle darstellt, war für reine Polymerheteroübergänge größer als für Polymer/Molekül-Heterostrukturen mit einem Minimum bei 0,5 eV. Drittens: parallel zum Aufbau der Akzeptor/Kathoden-Grenzfläche veränderte sich das Vakuumniveau um ca. 1 eV, bedingt durch das Pinning des Kathoden-Ferminiveaus (EF) an unbesetzte Grenzflächenzuständen. Die energetische Lage dieser Zustände bezüglich EF entschied dabei über die Stärke der Diffusionsspannung in der Solarzelle, welche bei Beleuchtung der entstandenen Solarzellenstruktur durch eine lichtinduzierte Photospannung ausgeglichen wurde. / The main focus of this work was to provide a comprehensive picture of the energy level alignment at the multitude of interfaces that occur in selected polymer/polymer and polymer/small molecule heterojunction photovoltaic cells. The electronic characterization was performed using photoelectron spectroscopy. Morphology and thickness of spin coated thin films was investigated using a complementary technique approach employing UV-vis absorption spectroscopy, atomic force microscopy, and X ray photoelectron spectroscopy. At the PEDT:PSS anode/polymer interface vacuum level shifts up to 0.65 eV were observed. Polymer deposition decreased the substrate work function (WF even though the polymer ionization energy was several 100 meV higher as the initial PEDT:PSS WF. An in depth analysis of the PEDT:PSS/polymer interface from sub-monolayer to multilayer coverage revealed highly diverse origins for the observed vacuum level shifts. Secondly, investigations of the donor/acceptor interfaces revealed vacuum level shifts up to 0.35 eV that influence the photovoltaic gap (PVG) at the heterojunction and, therefore, the upper limit of the open circuit voltage (VOC) in the device. Correlating device data and all results of the interface analysis, PVG was finally confirmed as an upper limit for VOC. The energy difference (eV) between PVG and experimentally determined VOC, which was assigned to losses in the device, was found to be higher for all polymer heterojunctions compared to polymer/small molecule cells with a minimum at eV = 0.5 eV. Third, cathode/acceptor interface formation was accompanied by interfacial vacuum level shifts of ca. 1 eV caused by Fermi level (EF) pinning at interfacial gap states. The exact position of the acceptor pinning level with respect to EF of the anode determines the strength of the built in field in the device that was found to be fully counterbalanced by a photovoltage induced by in situ illumination of the resulting OPVC-like sample structures.

Globally Asynchronous Locally Synchronous (GALS) Design ist eine Lösung zur Skalierbarkeit und Modularität für die SoC-Integration. Heutzutage ist GALS-Design weit in der Industrie angewendet. Die meisten GALS-Systeme basieren auf Dual-Clock-FIFOs für die Kommunikation Zwischen Taktdomänen. Um Leistungsverluste aufgrund der Synchronisationslatenzzeit zu vermindern, müssen die On-Chip-FIFOs ausreichend groß sein. Dies führt jedoch oft zu erheblichen Kosten-Hardware. Effiziente GALS- Lösungen sind daher vonnöten. Diese Arbeit berichtet unsere neuesten Fortschritte in GALS Design, das auf der Pausierenden Taktung basiert. Kritische Designthemen in Bezug auf Synchronisation-szuverlässigkeit bzw. Kommunikationsfähigkeit sind systematisch und analytisch un-tersucht. Ein lose gekoppeltes GALS Data-Link-Design wird vorgeschlagen. Es unter-stützt metastabilitätsfreie Synchronisation für Sub-Takt-Baum Verzögerungen. Außer-dem unterstützt es kontinuierliche Datenübertragung für High-Throughput-Kommuni-kation. Die Rosten hinsichtlich Energie verbrauch und Chipfläche sind marginal. GALS Design ist eingesetzt, um digitales On-Chip Umschaltrauschen zu verringern. Plesiochron Taktung mit balanciertem Leistungsverbrauch zwischen GALS Blöcken wird insbesondere untersucht. Für M Taktbereiche wird eine Reduzierung um 20lgM dB für die spektralen Spitzen des Versorgungsstroms bei der Takt-Grundfrequenz theoretisch hergcleitet. Im Vergleich zu den bestehenden synchronen Lösungen, geben diese Methode eine Alternative, um das digitale schaltrauschen effektiv zu senken. Schließlich wurde die entwickelte GALS Design Methodik schon bei reale Chip-Implementierungen angewendet. Zwei komplizierte industriell relevante Test-Chips, Lighthouse und Moonrake, wurden entworfen und mit State-Of-The-Art-Technologien hergestellt. Die experimentellen Ergebnisse bzw. / Globally asynchronous locally synchronous (GALS) design presents a solution of scalability and modularity to SoC integration. Today, it has been widely applied in the industry. Most of the GALS systems are based on dual-clock FIFOs for clock domain crossing. To avoid performance loss due to synchronization latency, the on-chip FIFOs need to be sufficiently large. This, however, often leads to considerable hardware costs. Efficient design solutions of GALS are therefore in great demand. This thesis reports our latest progress in GALS design bases on pausible clocking. Critical design issues on synchronization reliability and communication performance are studied systematically and analytically. A loosely-coupled GALS data-link design is proposed. It supports metastability-free synchronization for sub-cycle clock-tree delay, and accommodates continuous data transfer for high-throughput communication. Only marginal costs of power and silicon area are required. GALS design has been employed to cope with the on-chip digital switching noise in our work. Plesiochronous clocking with power-consumption balance between GALS blocks is in particular explored. Given M clock domains, a reduction of 20lgM dB on the spectral peaks of supply current at the fundamental clock frequency is theoretically derived. In comparison with the existing synchronous design solutions, it thus presents an alternative to effective attenuation of digital switching noise. The developed GALS design methodology has been applied to chip implementation. Two complicated industry-relevant test chips, named Lighthouse and Moonrake, were designed and fabricated using state-of-the-art technologies. The experimental results as well as the on-chip measurements are reported here in detail. We expect that, our work will contribute to the practical applications of GALS design based on pausible clocking in the industry.